CN102731354A - Preparation and plant growth-regulating activity of water-oil soluble o-(4-chloro) benzylthio-benzoate derivatives - Google Patents
Preparation and plant growth-regulating activity of water-oil soluble o-(4-chloro) benzylthio-benzoate derivatives Download PDFInfo
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Abstract
The invention provides water-oil soluble o-(4-chloro) benzylthio-benzoate derivatives with plant growth-regulating activity and salts thereof. The derivatives are shown as a general formula (I, II), wherein X is an oxygen atom, a nitrogen atom or a sulfur atom; n is 0, 1, 2, 3, 4, 5 and so on or (CH2)n represents alkyl carrying a branched chain; Y is Cl<->, Br<->, F<->, I<->, AcO<->, acetylsalicylic acid radical, nitric acid radical, salicylic acid radical, p-toluenesulfonic acid radical, bisulfate radical or other negative ions; R<1> is alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, alkenyl of 1-6 carbon atoms, or aryl; R<2> is alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, alkenyl of 1-6 atoms, or aryl; or R<1> and R<2> are selected from the structure in the specification.
Description
Technical field
The present invention relates to the preparation and the plant growth regulating activity of double neighbour-(4-chlorine) the benzylthio-benzoate derivatives that dissolves of a kind of novel water oil.
Background technology
The research of plant growth regulating substance starts from the discovery of nineteen twenty-eight growth hormone.
identified first natural hormone 3-indolyl acetic acid (IAA) in 1934; Find that it can promote the elongation of axis cell and promote cuttage root-taking; Found in succession again afterwards that some compounds also had tangible plant physiology regulating effect; And then the definition plant-growth regulator is meant that those can influence plant-growth, and can not make the lethal material of plant.Plant growth regulating substance can be divided into endogenous and exogenous two kinds; The former is commonly referred to as plant hormone; The latter is called plant-growth regulator, is the chemical substance of synthetic, and they not necessarily exist in plant materials; But have the effect similar, also can regulate growth and development of plant with plant hormone.
Now, plant-growth regulator has developed into big type of one in the agricultural chemicals.On function, can be divided into six big types, plant growth promoter, plant growth retardent, plant growth inhibitor, compound or Compositional type plant-growth regulator, preservation agent and male killing agent.Wherein, plant growth promoter can promote the growth of crop to make its raising the output, increases income, improves quality, consumption is few, pollution is little, do not have advantages such as resistance, and therefore, the research of plant-growth regulator enjoys investigator's concern.
Common plant rooting promoter have indolylacetic acid, indolebutyric acid, naphthylacetic acid etc. a few; And these several kinds of root-inducing promoters synthetic complicated, price is more expensive again, also shortcoming relatively of safety in utilization, can not satisfy agriculture prodn and environment protection to afforest, the requirement of artificial afforestration.Therefore to synthetic simple, low price, drug effect is high and the good novel root-inducing promoter of safety in utilization presses for very much.
In recent years, Chinese patent CN 1376672 has reported a kind of neighbour-substituted benzene (alkane) methylthio benzoic acid plant-growth regulator, and its chemical structure is as follows.
In the formula: X=H, chlorine is plain, alkoxyl group, nitro and alkyl etc.; N=0,1,2
Synthetic convenient, low, the good drug efficacy of cost of this class formation, and can effectively promote taking root of cucumber cotyledons.
CN 200610130710.1 has reported thio-ether type compounds plant growth regulator; Only reported that it is obvious especially for the cucumber cotyledons activity of taking root; And the conceptual neighbour of pointing out-thio-ether type compounds such as (4-chlorine) benzylthio-phenylformic acid have the effect that promotes plant establishment preferably, but do not relate to large-scale practical application such as nursery stock cottage propagation.Simultaneously, since simple neighbour-(4-chlorine) benzylthio-phenylformic acid, following molecular formula:
Water-soluble relatively poor, promote and use so influenced its big area.
CN 101700012 has reported again for the problem that solves neighbour-(4-chlorine) benzylthio-phenylformic acid poorly water-soluble and has kept the activity that neighbour-(4-chlorine) benzylthio-phenylformic acid promotes plant establishment again; Invented a kind of new plant growth regulating aqueous emulsion neighbour-(4-chlorine) benzylthio-benzoic acid preparation, i.e. 10% neighbour-(4-chlorine) benzylthio-phenylformic acid plant growth regulating aqueous emulsion.
In a word; At present about neighbour-substituted benzene (alkane) methylthio benzoic acid compounds and use the few of bibliographical information; But we can learn through above patent report: this reactive group of neighbour-(4-chlorine) benzylthio-phenylformic acid itself has the activity that promotes plant establishment; And simple in structure, synthetic easily, characteristics such as cost is low.But, and limited applying of it because the water-soluble and ester dissolubility of this class formation self is relatively poor.
The tradition pesticide formulation are main with missible oil, wettable powder, pulvis and granule; Be accompanied by the development and the exploitation of pesticides new formulation; Following can the development towards directions such as aqua, aqueous emulsion and microemulsions; From this development trend; This just has higher requirement to the novel pesticide molecule that is about to succeed in developing, not only want efficient, low toxicity, safety and and environmental friendliness, it is certain water-soluble to hope also that simultaneously drug molecule has; If drug molecule has good water-solubility and just can be made into aqua and directly use, so not only can reduce production costs but also can reduce when drug molecule is made into certain preparation to add the environmental pollution that high amounts of solvents, tensio-active agent, auxiliary agent and permeate agent etc. are brought.From this respect, the drug molecule good water-solubility has very important significance.Simultaneously, have certain water-soluble and fat-soluble drug molecule, it is necessary also to be that medicine effectively passes microbial film.
No matter medicine is that epidermis absorbs or other approach absorb, and all need pass barrier membranes with the form of molecule.Medicine needs at first dissolving, and if medicine have ideal biopharmacy characteristic, it is diffused into the zone of lower concentration from the zone of high density, stride across cytolemma and enter into the recycle system.All microbial films contain lipid as major ingredient.Active molecule all has and contains phosphatic high polar end structure in the biofilm structure, and, in most of the cases, two highly hydrophobic hydrocarbon chains.Microbial film has bilayer structure, and the hydrophilic chain end structure is towards the water zone of both sides.Very hydrophilic medicine can't pass biomembranous lipid layer and very hydrophobic medicine because the similar reason that mixes stops wherein as a biomembranous part, thereby can not effectively get into inner tenuigenin.
The objective of the invention is to make them can reach a good balance, reduce the outer loss of organism, thereby improve the utilization ratio of medicine through improving the water-soluble and fat-soluble of neighbour-substituted benzene (alkane) methylthio benzoic acid analog derivative.The novel cpd of these neighbour-substituted benzenes (alkane) methylthio benzoic acid analog derivative has two identical constructional features: they have part (oil soluble part) and the one-level that protonated form exists under physiology PH condition of a close ester property; Secondary, or tertiary amine group (water-soluble portion).Water-soluble-molten balance of oil like this is that medicine effectively passes microbial film institute necessary [Susan Milosovich, et al.J.Pharm.Sci., 82,227 (1993)].The amino that has positive charge has increased the solubleness of medicine greatly.This point can be seen from experimental implementation: in the product aftertreatment, the compound that does not become positive ion is dissolved in methylene dichloride and is water insoluble, add the hydrogen ion salify after, compound is dissolved in water layer, also is dissolved in methylene dichloride.As a rule, the solubleness of medicine is the step of the slowest and maximum speed limit in the absorption process.When these novel cpds are made medicament, in its molecule amino can with the phosphoric acid salt end group bonding of cytolemma.Therefore, thus very high these medicines that help of the partial concn of medicine in the microbial film outside through the zone of area with high mercury to lower concentration.After these drug molecules entered into microbial film, hydrophilic parts can promote the tenuigenin that medicine enters into the concentrated aqueous solution of semi liquid state.
Summary of the invention
It is active that the compound method that the purpose of this invention is to provide neighbour-substituted benzene (alkane) methylthio benzoic acid ester derivative and salt thereof, this compounds have excellent promotion plant-growth.
Shown in (I and II series), table 1 and table 2 represented to see in the chemical structural formula that part is concrete to the chemical structure of general formula of neighbour-substituted benzene (alkane) methylthio benzoic acid ester derivative and salt thereof as follows:
Wherein:
X represention oxygen atom, nitrogen-atoms, sulphur atom; N=0,1,2,3,4,5 ... Or (CH
2)
nRepresentative has the alkyl of side chain; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, or other negative ions.R
1Represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl or the aryl of a 1-6 carbon atom; R
2Represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl or the aryl of a 1-6 carbon atom; Or R
1, R
2Be selected from following structure:
The comparatively preferred compound of the present invention is:
N=1～4; X represents N, O, S; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, or other negative ions; R
1, R
2Be selected from H, C
1-C
4Alkyl or R
1=R
2Be selected from following structure:
General formula compound of the present invention (I, II) following method preparation:
Reaction path is following:
With midbody acid (A) and SOCl
2, PCl
3Or oxalyl chloride is dissolved in The suitable solvent, dioxane for example, benzene, toluene, ETHYLE ACETATE; THF, normal hexane, tetracol phenixin, chloroform or methylene dichloride; With organic bases such as pyridine, triethylamine is a catalyzer with DMF, temperature be 0 ℃ to boiling point down reaction made acyl chlorides (B) in 1-24 hour.
Acyl chlorides (B) and (n+1)-(dialkyl group) amino-1-alcohol (preparing), in The suitable solvent, temperature is 0 ℃ and reacts down to boiling point and to make product (I) in 1-24 hour.Solvent can be dioxane, benzene, toluene, ETHYLE ACETATE, THF, acetone, normal hexane, tetracol phenixin, chloroform or methylene dichloride etc.Add alkaline matter, like pyridine, triethylamine, sodium hydroxide, Pottasium Hydroxide, yellow soda ash, sodium hydrogencarbonate, salt of wormwood or saleratus etc. are to reacting favourable.
Product (I) and diluted acid YH can be dissolved in product (I) in the The suitable solvent, add diluted acid YH, and temperature is 0 ℃ and reacts down to boiling point and to make product (II) in 1-24 hour.Solvent can be dioxane, benzene, toluene, ETHYLE ACETATE, THF, acetone, normal hexane, tetracol phenixin, chloroform or methylene dichloride etc.
The present invention can also explain with the compound of listing in table 1, the table 2, but not limit the present invention.
Table 1: the The compounds of this invention of part shown in general formula I
Table 2: the The compounds of this invention of part shown in general formula I I
(I, II) compound has plant growth regulating activity to general formula of the present invention, can promote plant-growth.Compare with existing similar compound, this compounds shows better water-solubility and oil soluble and plant growth regulating activity.
The present invention comprises that also (I, II) compound is the plant growth regulator composition of active ingredient with general formula.The weight percentage of active ingredient is 1-99% in this plant-growth regulator component.Comprise also in this plant growth regulator composition that agricultural goes up acceptable carrier.
General formula (I of the present invention; II) compound and can process several formulations as the plant growth regulator composition of active ingredient and use, especially general formula (II) can directly be made into aqua and use; Both reduced with an organic solvent the pollution of environment, be more conducive to absorption and the conduction of plant again.In these compsns, also can add the liquid or solid carrier, and add an amount of tensio-active agent and come compounding application.
Other embodiment of the present invention is the method for use of plant-growth regulator, and this method comprises compound of the present invention and compsn thereof are applied to said plant and seed, or on the surface of its growth medium.Amount of application is generally per hectare 15 and restrains 200 grams, and preferred significant quantity is that per hectare 30 restrains 100 grams.In addition, also can add one or more other plant-growth regulator in compound of the present invention and in the active composition, can produce effect more efficiently thus.
(I, II) compound both can use separately as plant-growth regulator and also can cooperate other known sterilant, sterilant, plant-growth regulator or fertilizer to be mixed together use general formula of the present invention.
Should be clear and definite be in claim scope of the present invention, can carry out various changes and conversion as required.
Embodiment
The following example is tested the result with living test can further be used for explaining the plant growth regulating activity of compound of the present invention, but does not mean that restriction the present invention.
Synthetic embodiment
Compound 1:2 '-N, N-dimethyl--2-(4-chlorine) benzylthio-ethyl benzoate synthetic
In the 100mL round-bottomed flask, add 2.785g (0.01mol) neighbour-(4-chlorine) benzylthio-phenylformic acid and 10ml sulfur oxychloride, reflux 8h cools off then, and decompression steams unnecessary sulfur oxychloride, gets taupe solid neighbour-(4-chlorine) benzylthio-Benzoyl chloride 99min..
In the above-mentioned 100mL round-bottomed flask that fills the 0.01mol acyl chlorides that has prepared; Add the 20mL methylene dichloride and make the acyl chlorides dissolving, under ice bath, slowly drip 0.89g N, the mixed solution of N-dimethylethanolamine, 1.5mL triethylamine and 15ml methylene dichloride then; Dropwise; Stirred overnight at room temperature, the TLC detection reaction is complete, with saturated NaHCO
3The aqueous solution is neutralized to PH=7.5～8.5, tells organic phase.Anhydrous sodium sulfate drying, the pressure reducing and steaming solvent gets reddish black viscous fluid resistates, through column chromatography [V
Sherwood oil/ V
ETHYLE ACETATE=4/1, add a little triethylamine] separate and obtain deep yellow solid chemical compound 1,67～69 ℃ of mp, yield 52.9%.
1H?NMR(400MHz，CDCl
3)δ：2.34(s，6H，2C
H 3)，2.76(t，2H，J
H＝5.6Hz，C
H 2)，4.05(s，2H，C
H 2)，4.41(t，2H，J
H＝5.6Hz，C
H 2)，7.10(t，1H，J
H＝7.6Hz，Ar
H)，7.26(d，2H，J
H＝8.4Hz，2Ar
H)，7.33(t，1H，J
H＝7.2Hz，Ar
H)，7.21(d，3H，J
H＝5.2Hz，3Ar
H)，7.91(d，1H，J
H＝7.6Hz，Ar
H)；HRMS：calc?for?C
18H
20NO
2SCl；(M+H)
+350.0976；Found?350.0979。
Compound 2:2 '-N, N-diethylammonium-2-(4-chlorine) benzylthio-ethyl benzoate synthetic
Compound method gets white solid compound 2,42～43 ℃ of mp, yield 49.54% with compound 1.
1H?NMR(400Hz，CD
3Cl)δ：1.09(t，6H，J
H＝7.2Hz，CH
2C
H 3)，2.67(q，4H，J
H＝7.2Hz，C
H 2CH
3)，2.89(t，2H，J
H＝6.4Hz，C
H 2 )，4.13(s，2H，C
H 2 )，4.43(t，2
H，J
H＝6.4Hz，C
H 2)，7.16-7.20(m，1H，Ar
H)，7.27-7.30(m，3H，3Ar
H)，7.34-7.36(m，2H，2Ar
H)，7.39-7.43(m，1H，Ar
H)，7.98-8.00(m，1H，Ar
H)；HRMS：calc?for?C
20H
24NO
2SCl；(M+H)
+378.1289；Found?378.1284。
Compound 3:2 '-N, N-di-isopropyl-2-(4-chlorine) benzylthio-ethyl benzoate synthetic
Compound method gets white solid compound 3,73～76 ℃ of mp, yield 51.05% with compound 1.
1H?NMR(400Hz，CD
3Cl)δ：0.98(s，12H，CHC
H 3)，2.72(br，2H，C
HCH
3)，2.98(br，2H，C
H 2 )，4.05(s，2H，C
H 2)，4.19(br，2H，C
H 2)，7.09(t，1H，J
H＝7.6Hz，Ar
H)，7.21(d，3H，J
H＝8.0Hz，3Ar
H)，7.27(d，2H，J
H＝8.4Hz，2Ar
H)，7.32(t，1H，J
H＝7.6Hz，Ar
H)，7.92(t，1H，J
H＝8.0Hz，Ar
H)；HRMS：calc?forC
22H
28NO
2SCl；(M+H)
+406.1602；Found?406.1595。
Synthesizing of compound 6:2-(4-chlorine) benzylthio-phenylformic acid morpholine ethanol ester
Compound method gets white solid compound 6,97～98 ℃ of mp, yield 42.66% with compound 1.
1H?NMR(400Hz，CD
3Cl)δ：2.63(t，4H，J
H＝4.4Hz，C
H 2)，2.84(t，2H，J
H＝5.2Hz，CH
2)，3.76(t，4H，J
H＝4.4Hz，C
H 2 )，4.14(s，2H，C
H 2 )，4.51(t，2H，J
H＝5.2Hz，C
H 2)，7.20(t，1H，J
H＝7.2Hz，Ar
H)，7.31(d，3H，J
H＝5.6Hz，3Ar
H)，7.36(d，2H，J
H＝8.4Hz，2Ar
H)，7.44(t，1H，J
H＝6.8Hz，Ar
H)，7.98(q，1H，J
H＝6.4Hz，Ar
H)；HRMS：calc?for?C
20H
22NO
3SCl；(M+H)
+392.1085；Found?392.1088。
Compound 15:2 '-N, N-dimethyl--2-(4-chlorine) benzylthio-BM synthetic
Compound method gets Off-white solid compound 15,37～39 ℃ of mp, yield 49.24% with compound 1.
1H?NMR(400MHz，CD
3Cl)δ：2.26(s，6H，2C
H 3)，2.51(t，2
H，J
H＝6.0Hz，C
H 2N)，3.53(dd，2H，J
H＝5.6Hz，J
H?＝11.2Hz，NHC
H 2)，4.08(s，2H，ArC
H 2)，6.87(br，1H，N
H)，7.19-7.28(m，7H，Ar
H)，7.57(d，1H，J
H＝6.8Hz，Ar
H)；HRMS：calc?for?C
18H
21N
2OSCl；(M+H)
+349.1136；Found?349.1135。
Compound 1-H:2 '-N, N-dimethyl--2-(4-chlorine) benzylthio-ethyl benzoate hydrochloride synthetic
In the 50mL round-bottomed flask, add 2 '-N, N-dimethyl--2-(4-chloro benzyl sulfur) ethyl benzoate (compound 1) 0.45g (0.00129mol) and 15mL methylene dichloride; Induction stirring makes its dissolving; Under ice bath, slowly feed exsiccant HCl gas then, logical continuously 0.5h can react completely, and removes methylene dichloride and gets milk yellow solid chemical compound 1-H; 165～168 ℃ of mp, yield 98.8%.
1H?NMR(400MHz，CD
3Cl)δ：2.90(s，6H，2C
H 3)，3.46(br，2H，C
H 2)，4.13(s，2H，C
H 2)，4.83(br，2H，C
H 2)，7.23(br，1H，Ar
H)，7.30(br，5H，5Ar
H)，7.46(br，1H，Ar
H)，8.04(br，1H，Ar
H)；HRMS：calc?for?C
18H
21NO
2SCl
2；M
+350.0976；Found?350.0978。
Compound 2-H:2 '-N, N-diethylammonium-2-(4-chlorine) benzylthio-ethyl benzoate hydrochloride synthetic
Compound method gets white solid compound 2-H, 142～146 ℃ of mp, yield 100% with compound 1-H.
1H?NMR(400MHz，CD
3Cl)δ：2.90(s，6H，2C
H 3)，3.46(br，2H，C
H 2)，4.13(s，2H，C
H 2)，4.83(br，2H，C
H 2)，7.23(br，1H，Ar
H)，7.30(br，5H，5Ar
H)，7.46(br，1H，Ar
H)，8.04(br，1H，Ar
H)；HRMS：calc?forC
18H
21NO
2SCl
2；M
+350.0976；Found?350.0978。
Compound 3-H:2 '-N, N-di-isopropyl-2-(4-chlorine) benzylthio-ethyl benzoate hydrochloride synthetic
Compound method gets white solid compound 3-H, 169～172 ℃ of mp, yield 98.8% with compound 1-H.
1H?NMR(400MHz，CD
3Cl)δ：1.40(d，6H，J
H＝6.0Hz，2C
H 3)，1.49(d，6H，J
H＝6.0Hz，2C
H 3)，3.24(br，2H，C
H 2)，3.63(br，2H，2C
H)，4.06(s，2H，C
H 2 )，4.89(br，2H，C
H 2 )，7.14(t，1H，J
H＝7.2Hz，Ar
H)，7.20-7.28(m，5H，5Ar
H)，7.38(t，1H，J
H＝7.6Hz，Ar
H)，7.99(d，1H，J
H＝7.2Hz，Ar
H)，11.89(br，1H，N
H)；HRMS：calc?for?C
22H
29NO
2SCl
2；M
+406.1602；Found?406.1607。
Synthesizing of compound 6-H:2-(4-chlorine) benzylthio-phenylformic acid morpholine ethanol ester hydrochloride
Compound method gets white solid compound 6-H, 152～155 ℃ of mp, yield 98.9% with compound 1-H.
1H?NMR(400MHz，CD
3Cl)δ：2.88(d，2H，J
H＝9.6Hz，C
H 2)，3.33(br，2H，C
H 2)，3.45(d，2H，J
H＝11.6Hz，C
H 2)，3.87(d，2H，J
H＝10.8Hz，C
H 2 )，4.04(s，2H，C
H 2 )，4.21(t，2H，J
H＝12.0Hz，C
H 2 )，4.83(br，2H，C
H 2 )，7.13(t，1H，J
H＝7.2Hz，Ar
H)，7.17-7.25(m，5H，5Ar
H)，7.37(t，1H，J
H＝7.2Hz，Ar
H)，7.88(d，1H，J
H＝7.2Hz，Ar
H)，13.58(br，1H，N
H)；HRMS：calc?for?C
20H
23NO
3SCl
2；M
+392.1082；Found?392.1085。
Synthesizing of compound 15-H:2-(4-chlorine) benzylthio-benzamide hydrochloride salt
Compound method gets white solid compound 15-H, 52～55 ℃ of mp, yield 99.4% with compound 1-H.
1H?NMR(400MHz，CD
3Cl)δ：2.86(s，6H，2C
H 3)，3.31(br，2H，C
H 2N)，3.87(br，2H，NHC
H 2)，4.10(s，2H，ArSC
H 2)，7.23-7.33(m，7H，Ar
H)，7.75(d，1H，J
H＝6.4Hz，Ar
H)，8.31(br，1H，N
H)，12.05(br，1H，R
3N-
H)；HRMS：calc?for?C
18H
22N
2OSCl
2；M
+349.1139；Found?349.1142。
Other compound all can obtain through similar approach in table 1, the table 2.
Give birth to and survey instance:
Target compound has been carried out the test of taking root of rape hypocotyls elongation test, wheat bud scale elongation test, cucumber cotyledons augmentation test and cucumber cotyledons respectively.
Rape hypocotyls elongation test method: supplying formation testing vegetable kind is that May is climing.After the seed soaking, the seed of selecting uniformity is for use.Weighing 3mg sample is dissolved among the 3mL DMF then, dilutes 10 times, gets 0.2mL again and evenly drips on the filter paper of diameter 6cm; After treating that solvent is air-dry, in the petridish of diameter 6cm, put into 1 of the filter paper that contains sample, add zero(ppm) water 2mL; Be made into the soup of 10 μ g/mL, the seed with 10 uniformities is placed on the filter paper that contains sample uniformly at last, is contrast with zero(ppm) water, places under 25 ℃ of dark surrounds to cultivate; Measure hypocotyl length behind the 72h, every processing repeats for 2 times, the record result.
Wheat bud scale elongation test method: supply the examination wheat breed to resist No. 6 for wheel.Seed soaking back sowing places and cultivates 72h 25 ℃ of dark surrounds under in containing the enamel tray with cover of 0.7% agar, when treating that the seedling height is 2.5～3.0cm, removes the vertical 3mm of bud scale, cuts the 5mm sheath segment that sprouts, and places zero(ppm) water 1h, with the removal endogenous hormones.Weighing 3mg sample is dissolved among the 3mLDMF then, dilutes 10 times; Get 0.3mL again and evenly drip on the filter paper of diameter 6cm, treat that solvent is air-dry after, in the petridish of diameter 6cm; Put into 1 of the filter paper that contains sample; Add 0.01mol/L phosphoric acid-citrate buffer solution (PH=5) 3mL that contains 2% sucrose, evenly put into 10 segments, be 10 μ g/mL chemicals treatment.Be contrast with phosphoric acid-citrate buffer solution then, place under 25 ℃ of dark surrounds and cultivate that measure per 10 length that segment is total behind 18～20h, every processing repeats for 2 times, the record result.
Cucumber cotyledons augmentation test method: supplying the examination cucumber variety is that grind No. 4 in Tianjin.The sowing of seed soaking back places and cultivates 72h under 26 ℃ of dark surrounds in filling the enamel tray with cover of 0.7% agar, and the cotyledon of selected big or small uniformity is for use.Weighing 3mg sample is dissolved among the 3mL DMF then, dilutes 10 times, gets 0.3mL again and evenly drips on the filter paper of diameter 6cm; After treating that solvent is air-dry, in the petridish of diameter 6cm, put into 1 of the filter paper that contains sample; Add zero(ppm) water 3mL, 10 of cotyledons are 10 μ g/mL and handle.Be contrast at last with zero(ppm) water.Place 26 ℃, the 3000Lux environment is cultivated down, measures per 10 slice, thin piece leaf fresh weights behind the 72h.Every processing repeats for 2 times, the record result.
The cucumber cotyledons test method(s) of taking root: supplying the examination cucumber variety is that grind No. 4 in Tianjin.Be sowed at after the seed soaking in the enamel tray with cover that fills 0.7% agar, place and cultivate 72h under 26 ℃ of dark surrounds, the cotyledon of selected big or small uniformity is for use.Weighing 3mg sample is dissolved among the 3mLDMF then, dilutes 10 times, gets 0.3mL again and evenly drips on the filter paper of diameter 6cm; After treating that solvent is air-dry, in the petridish of diameter 6cm, put into 1 of the filter paper that contains sample; Add zero(ppm) water 3mL, 10 of cotyledons are 10 μ g/mL and handle.Be contrast at last with zero(ppm) water.Place under 26 ℃ of dark surrounds and cultivate, measure the number of taking root of per 10 slice, thin piece petiole bases behind the 5d.Every processing repeats for 2 times, the record result.
Part of compounds test result such as following table:
The plant growth regulating activity of part target compound is measured the result
Z
13* be known compound 2-(4-chlorine) benzylthio-phenylformic acid.
Claims (5)
1. water oil neighbour-(4-chlorine) the benzylthio-benzoate derivatives and salt thereof of holding concurrently and dissolving, as general formula (I, II) shown in:
Wherein:
X represention oxygen atom, nitrogen-atoms, sulphur atom; N=0,1,2,3,4,5 ... Or (CH
2)
nRepresentative has the alkyl of side chain; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, or other negative ions.R
1Represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl or the aryl of a 1-6 carbon atom; R
2Represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl or the aryl of a 1-6 carbon atom; Or R
1, R
2Be selected from following structure:
2. compound as claimed in claim 1 is characterized in that, general formula (I, II) in:
N=1～4; X represents N, O, S; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, or other negative ions; R
1, R
2Be selected from H, C
1-C
4Alkyl or R
1=R
2Be selected from following structure:
3. the described compound of claim 1 or its compsn are used to promote the purposes of plant-growth.
4. a plant growth regulators mixture contains compound as claimed in claim 1 and goes up acceptable carrier with agricultural, and the weight percentage of active ingredient is 1-99% in the compsn.
5. the method for a regulating plant growth is characterized in that: to the plant-growth regulator mixture as claimed in claim 4 of plant seed and foliage applying significant quantity.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376672A (en) * | 2002-04-16 | 2002-10-30 | 南开大学 | O-substituted benzene (alkyl) sulfenyl benzoic acid as plant growth regulator |
| CN100998328A (en) * | 2006-12-30 | 2007-07-18 | 南开大学 | Thio-ether type compounds plant growth regulator |
| CN101700012A (en) * | 2009-11-05 | 2010-05-05 | 南开大学 | O-(4-chloro) benzylthio benzoic acid preparation and preparation method as well as application |
-
2012
- 2012-07-10 CN CN2012102359467A patent/CN102731354A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376672A (en) * | 2002-04-16 | 2002-10-30 | 南开大学 | O-substituted benzene (alkyl) sulfenyl benzoic acid as plant growth regulator |
| CN100998328A (en) * | 2006-12-30 | 2007-07-18 | 南开大学 | Thio-ether type compounds plant growth regulator |
| CN101700012A (en) * | 2009-11-05 | 2010-05-05 | 南开大学 | O-(4-chloro) benzylthio benzoic acid preparation and preparation method as well as application |
Non-Patent Citations (1)
| Title |
|---|
| 王瑞花: "新型水油兼溶绿色环保直用型农药分子的设计、合成及生物活性研究", 《南开大学硕士学位论文》 * |
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